CN110556221B - Single crystal-like heterojunction room temperature magnetic refrigeration material with large magnetic entropy change and wide working temperature zone and preparation process thereof - Google Patents

Single crystal-like heterojunction room temperature magnetic refrigeration material with large magnetic entropy change and wide working temperature zone and preparation process thereof Download PDF

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CN110556221B
CN110556221B CN201910742765.5A CN201910742765A CN110556221B CN 110556221 B CN110556221 B CN 110556221B CN 201910742765 A CN201910742765 A CN 201910742765A CN 110556221 B CN110556221 B CN 110556221B
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single crystal
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CN110556221A (en
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刘丹敏
王少博
梁允田
徐国梁
张振路
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Beijing University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/02—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method without using solvents
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/52—Alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
    • H01F1/015—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets

Abstract

The invention relates to Mn with large magnetic entropy change and wide working temperature zone5Ge3/(Mn,Fe)5Ge3A single crystal heterojunction-like room temperature magnetic refrigeration material and a preparation process thereof. Simple substances of Mn, Fe, P, Ge and Sn are used as raw materials according to Mn2‑xFexP1‑yGeySn12(x is more than or equal to 0.80 and less than or equal to 0.90, and y is more than or equal to 0.20 and less than or equal to 0.26) mixing the raw materials and packaging in a quartz tube filled with Ar gas, and successfully preparing the acicular Mn with the diameter of about 100-300 mu m and the length of 1cm for the first time through the processes of high-temperature heat preservation, slow cooling, molten metal Sn pouring, acid pickling separation and the like5Ge3/(Mn,Fe)5Ge3A single crystal heterojunction-like room temperature magnetic refrigeration material. The room temperature magnetic refrigeration material has the advantages of large magnetic entropy change, wide working temperature area, large refrigeration capacity, no need of subsequent processing, acid corrosion resistance and the like, and can be directly used as a room temperature magnetic refrigeration working medium.

Description

Single crystal-like heterojunction room temperature magnetic refrigeration material with large magnetic entropy change and wide working temperature zone and preparation process thereof
Technical Field
The invention relates to a magnetic refrigeration material and a preparation process thereof.
Background
Magnetic refrigeration is a green environment-friendly refrigeration technology, and the basic principle is as follows: the method is characterized in that a magnetic material is used as a refrigerating working medium, isothermal magnetization heat release and adiabatic demagnetization heat absorption are utilized to refrigerate, namely a Carnot cycle mode is constructed based on a magnetocaloric effect to achieve the refrigerating effect. The gas compressor has the advantages of high efficiency, energy conservation, high reliability, no greenhouse effect, ozone layer damage and the like, and is expected to replace the traditional gas compression refrigeration technology. Has important significance for the sustainable coordination development of human society and environment/nature.
In recent years, magnetic refrigeration materials based on the magnetocaloric effect at room temperature have been widely studied and rapidly developed. At present, the most studied mainly includes MnFePGe/Si series compounds, La (Fe, Si)13Series compounds and transition intermetallic compounds having martensitic transformation such as NiMnGa, MnCoGe, etc. Although the compounds have first-order magnetic phase change near room temperature, and the phase change is accompanied by giant magnetocaloric effect, so that the refrigeration is very favorable, the compounds have larger thermal hysteresis and magnetic hysteresis, and are unfavorable for the refrigeration. In addition, the working temperature zone is very narrow (generally only dozens of degrees), so that the compound can only work efficiently in a very small temperature range, which seriously influences the actual refrigeration power of the compound as a magnetic working medium and hinders the step of practical application. In addition, most of the magnetic working media used for magnetic refrigeration equipment at present need to be processed into spherical particles smaller than 1mm or thinner sheets to increase the surface area, so as to enhance the heat exchange between the magnetic working media and the fluid medium, and finally further improve the refrigeration power and efficiency. However, almost all magnetic refrigeration materials belong to hard and brittle intermetallic compounds, and the processing is difficult, so that the processing cost of the magnetic working medium is high, and the popularization of the future magnetic refrigeration technology is not facilitated.
Therefore, the room temperature magnetic refrigeration material which has large magnetocaloric effect, wide working temperature area and large refrigeration capacity, does not need subsequent processing and is resistant to acid corrosion is prepared, and the room temperature magnetic refrigeration technology can be greatly promoted to be in the way of practical application.
Disclosure of Invention
The invention aims to provide Mn which has a working temperature near room temperature, has a large magnetocaloric effect, a wide working temperature region and large refrigerating capacity in the magnetic field range of a permanent magnet, does not need subsequent processing, is resistant to acid corrosion and can be widely applied to the magnetic refrigeration technology5Ge3/(Mn,Fe)5Ge3A monocrystal-like heterojunction magnetic refrigeration material and a preparation process thereof.
Preparation of Mn in accordance with the invention5Ge3/(Mn,Fe)5Ge3The formula of the single crystal heterojunction-like room temperature magnetic refrigeration material is as follows: mn2-xFexP1-yGeySn12Wherein x is in the range: 0.80-0.90, y is in the range of: 0.20 to 0.26.
The technical scheme of the invention is that high-purity simple substances Mn, Fe, P, Ge and Sn are used as raw materials, the raw materials are mixed and packaged in a quartz tube filled with Ar gas according to the component proportion of the formula, and Mn is prepared by the processes of high-temperature heat preservation, slow cooling, molten metal Sn pouring, acid washing separation and the like5Ge3/(Mn,Fe)5Ge3A single crystal heterojunction-like room temperature magnetic refrigeration material. The method comprises the following specific steps:
(1) using 99.99% -99.9999% high-purity block simple substances Mn, Fe, P, Ge and Sn as raw materials, and putting the raw materials in a glove box with high-purity Ar gas protection according to Mn2-xFexP1-yGeySn12Compounding, mixing and filling high-purity Al2O3And then fixing the crucible in a high-purity quartz tube by adopting high-purity quartz cotton, placing a separating device paved with the high-purity quartz cotton at the opening of the crucible, filling high-purity Ar gas into the quartz tube for protection and increasing the vapor pressure to reduce the volatilization of the raw materials, and finally sealing the quartz tube.
(2) And (3) putting the sealed quartz tube into a muffle furnace, heating to 1173K from room temperature, preserving heat for 3-7 days to ensure that Mn, Fe, P and Ge are fully dissolved in the Sn melt, then slowly cooling to 573K at a cooling rate of 4-6K/h to ensure balanced and stable growth of crystals, then taking the quartz tube out of the muffle furnace, inversely pouring molten metal Sn, and fully filtering through quartz wool until the molten metal Sn is fully cooled.
(3) Taking out the Sn-coated pseudo-single crystal, putting the Sn-coated pseudo-single crystal into a dilute hydrochloric acid solution with the concentration of 10 percent (mass fraction), soaking for 1-2 weeks, filtering out the solution, and washing the separated pseudo-single crystal with distilled water and alcohol for multiple times to obtain acicular Mn which has almost no corrosion signs and has mirror surface luster on the surface5Ge3/(Mn,Fe)5Ge3A single crystal-like heterojunction, as shown in figure 1. FIG. 2 shows Mn5Ge3/(Mn,Fe)5Ge3The XRD diffraction patterns and interpolation patterns of the single-crystal-like heterojunction and the crushed powder thereof are respectively a Scanning Electron Microscope (SEM) morphology pattern and a single-crystal XRD diffraction pattern. The results show that the crystal structure from the inside to the surface of the crystal is the same as that of hexagonal Mn except for Sn (white area in SEM morphology) which is not completely etched off from the surface of the crystal5Ge3Has the same crystal structure and the growth direction is along the c-axis [001 ]]Direction, but it is not a perfect single crystal, belonging to the single-crystal-like (single-crystal-like) family.
The invention mainly has the following characteristics:
1. the acicular Mn with the diameter of 100-300 mu m and the maximum length of 1cm is successfully prepared for the first time5Ge3/(Mn,Fe)5Ge3A quasi-single crystal heterojunction. In addition, the single crystal-like heterojunction can be repeatedly prepared according to the proportion and the preparation process.
2. The heterojunction has the working temperature near the room temperature, has large magnetic thermal effect, wide working temperature area and large refrigerating capacity in the magnetic field range of the permanent magnet, does not need subsequent processing and acid corrosion resistance, can be directly used as a magnetic working medium in room temperature magnetic refrigeration equipment, can improve the actual refrigerating power and efficiency of the magnetic refrigeration equipment, and accelerates the room temperature magnetic refrigeration step toward practical application.
Description of the drawings:
FIG. 1 shows Mn5Ge3/(Mn,Fe)5Ge3A quasi-single crystal heterojunction.
FIG. 2 shows Mn5Ge3/(Mn,Fe)5Ge3The XRD diffraction patterns and interpolation patterns of the single-crystal-like heterojunction and the crushed powder thereof are respectively a Scanning Electron Microscope (SEM) morphology pattern and a single-crystal XRD diffraction pattern.
FIG. 3 shows Mn prepared in example 15Ge3/(Mn,Fe)5Ge3The cross section microstructure (a) of the single crystal-like heterojunction and the EDS mapping (b-f) of Mn, Fe, Ge, Sn, P and other elements.
FIG. 4 shows Mn prepared in example 15Ge3/(Mn,Fe)5Ge3The relationship curve of the magnetic entropy change and the temperature of the single crystal-like heterojunction.
FIG. 5 shows Mn prepared in example 25Ge3/(Mn,Fe)5Ge3The cross section microstructure (a) of the single crystal-like heterojunction and the EDS mapping (b-f) of Mn, Fe, Ge, Sn, P and other elements.
FIG. 6 shows Mn prepared in example 35Ge3/(Mn,Fe)5Ge3The cross section microstructure (a) of the single crystal-like heterojunction and the EDS mapping (b-f) of Mn, Fe, Ge, Sn, P and other elements.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1 starting from 99.99% Mn and Fe blocks, 99.9999% Red P and 99.999% Ge blocks and Sn balls, according to Mn1.15Fe0.85P0.74Ge0.26Sn12The formula is proportioned and is filled with Al after being mixed2O3The crucible was sealed in a quartz tube filled with Ar gas. And putting the sealed quartz tube into a muffle furnace, heating to 1173K from room temperature, preserving the heat for 7 days, then slowly cooling to 573K at a cooling rate of 5K/h, taking the quartz tube out of the muffle furnace, inversely pouring molten metal Sn, and fully filtering through quartz wool until the molten metal Sn is completely cooled. Taking out the Sn-coated pseudo-single crystal, soaking the Sn-coated pseudo-single crystal in a 10% (mass fraction) diluted hydrochloric acid solution for 1-2 weeks, filtering the solution, and cleaning the separated pseudo-single crystal with distilled water and alcohol for multiple times to obtain needle-shaped Mn5Ge3/(Mn,Fe)5Ge3A quasi-single crystal heterojunction.
A cross-sectional sample of the single-crystal-like heterojunction embedded in the Sn melt was prepared by mechanical polishing combined with Ar ion polishing, and the composition and distribution of the components of the sample were analyzed by an energy spectrometer (EDS) configured in a Scanning Electron Microscope (SEM), as shown in fig. 3. The results show that there is no Sn and P in the crystal except for the existence of cracks or primary holes generated by the fracture of the center of the crystal section during mechanical polishing, which leads to the very soft Sn mosaic of the clad metalBut consists of three elements of Mn, Fe and Ge; in addition, Ge is completely uniformly distributed over the entire cross section, Fe is uniformly distributed in the central region of the cross section, and a part of Mn in the central region is substituted, resulting in a lower content of Mn in the central region of the cross section than in the edge region and a uniform distribution in the corresponding region. Therefore, this distribution of the three elements creates a distinct compositional boundary, confirming that the crystal belongs to a homostructural single crystal-like heterojunction (or core-shell structure). Measuring the Mn of the heterojunction at 280-340K (Mn in the heterojunction) by using a component Vibration Sample Magnetometer (VSM) of a Physical Property Measurement System (PPMS)5Ge3Has a Curie temperature of 300K, (Mn, Fe)5Ge3The Curie temperature of 332K), the magnetic entropy change (-Delta S) of the heterojunction is calculated according to Maxwell' S equation, and the working temperature zone (Delta T) is calculatedFWHM: temperature span at half maximum of magnetic entropy change) and cooling capacity (RC: maximum magnetic entropy change multiplied by operating temperature zone) as shown in fig. 4. The magnetic entropy of the heterojunction is maximized near 300K, a large magnetic entropy change value is kept in a wide temperature range, the heterojunction takes a table shape, and obvious anisotropy is shown, namely the magnetic entropy of H// c is larger than that of H// a; in addition, with the increase of an external magnetic field, the magnetic entropy change, the working temperature area and the refrigerating capacity of the heterojunction are correspondingly increased. When H// c is obtained, the magnetic entropy changes of the heterojunction under the external fields of 0-1T, 0-2T and 0-3T are respectively 1.36, 2.22 and 2.96J/kg.K, the working temperature regions are respectively 48, 54 and 57K, and the refrigerating capacity is respectively 65, 120 and 169J/kg. As can be seen, Mn5Ge3/(Mn,Fe)5Ge3The quasi-single crystal heterojunction is a room temperature magnetic refrigeration material which has large magnetocaloric effect, wide working temperature area and large refrigeration capacity in the magnetic field range of the permanent magnet, does not need subsequent processing and is resistant to acid corrosion, and can be directly used as a magnetic working medium in room temperature magnetic refrigeration equipment.
Example 2 starting from 99.99% Mn and Fe blocks, 99.9999% Red P and 99.999% Ge blocks and Sn balls, according to Mn1.10Fe0.90P0.80Ge0.20Sn12The formula is proportioned and is filled with Al after being mixed2O3The crucible is sealed with the stone filled with Ar gasIn the quartz tube. And putting the sealed quartz tube into a muffle furnace, heating to 1173K from room temperature, preserving the heat for 3 days, then slowly cooling to 573K at a cooling rate of 4K/h, taking the quartz tube out of the muffle furnace, inversely pouring molten metal Sn, and fully filtering through quartz wool until the molten metal Sn is completely cooled. Taking out the Sn-coated pseudo-single crystal, soaking the Sn-coated pseudo-single crystal in a 10% (mass fraction) diluted hydrochloric acid solution for 1-2 weeks, filtering the solution, and cleaning the separated pseudo-single crystal with distilled water and alcohol for multiple times to obtain needle-shaped Mn5Ge3/(Mn,Fe)5Ge3A quasi-single crystal heterojunction. A cross-sectional sample of the single-crystal-like heterojunction embedded in the Sn melt was prepared by mechanical polishing combined with Ar ion polishing, and the composition and distribution of the components of the sample were analyzed by an energy spectrometer (EDS) configured in a Scanning Electron Microscope (SEM), as shown in fig. 5. As in example 1, it was confirmed that the crystal belongs to a homostructural single crystal-like heterojunction (or core-shell structure). Mn prepared according to the formula5Ge3/(Mn,Fe)5Ge3The single crystal-like heterojunction has similar magnetocaloric performance to example 1, and can also be directly used as a magnetic working medium in room-temperature magnetic refrigeration equipment.
Example 3 starting from 99.99% Mn and Fe blocks, 99.9999% Red P and 99.999% Ge blocks and Sn balls, according to Mn1.20Fe0.80P0.74Ge0.26Sn12The formula is proportioned and is filled with Al after being mixed2O3The crucible was sealed in a quartz tube filled with Ar gas. And putting the sealed quartz tube into a muffle furnace, heating to 1173K from room temperature, preserving the heat for 5 days, then slowly cooling to 573K at a cooling rate of 6K/h, taking the quartz tube out of the muffle furnace, inversely pouring molten metal Sn, and fully filtering through quartz wool until the molten metal Sn is completely cooled. Taking out the Sn-coated pseudo-single crystal, soaking the Sn-coated pseudo-single crystal in a 10% (mass fraction) diluted hydrochloric acid solution for 1-2 weeks, filtering the solution, and cleaning the separated pseudo-single crystal with distilled water and alcohol for multiple times to obtain needle-shaped Mn5Ge3/(Mn,Fe)5Ge3A quasi-single crystal heterojunction. Preparing a cross-section sample of a single-crystal-like heterojunction embedded in a Sn melt by adopting mechanical polishing combined with Ar ion polishingThe composition and distribution of the components of the sample were analyzed by an energy spectrometer (EDS) equipped in a Scanning Electron Microscope (SEM), as shown in fig. 6. As in example 1, it was confirmed that the crystal belongs to a homostructural single crystal-like heterojunction (or core-shell structure). Mn prepared according to the formula5Ge3/(Mn,Fe)5Ge3The single crystal-like heterojunction has similar magnetocaloric performance to example 1, and can also be directly used as a magnetic working medium in room-temperature magnetic refrigeration equipment.
The results show that the magnetic refrigeration material which can work near room temperature, has large magnetocaloric effect, wide working temperature region and large refrigeration capacity in the magnetic field range of the permanent magnet, does not need subsequent processing and is resistant to acid corrosion is efficiently prepared, and the actual refrigeration power and efficiency of the magnetic refrigeration equipment can be effectively improved. Particularly, the invention provides a practical and effective scheme for overcoming the bottleneck of the current magnetic refrigeration technology, and can accelerate the stepping of the magnetic refrigeration technology to practical steps.
Any method of equivalent substitution or change of the technical solution and the inventive concept thereof should be covered within the protection scope of the present invention.

Claims (1)

1. The single crystal-like heterojunction room temperature magnetic refrigeration material is characterized in that: mn x2-Fe x P y1-Ge y Sn12WhereinxThe range of (A) is as follows: 0.80 to 0.90 percent of a total,ythe range of (A) is as follows: 0.20 to 0.26;
the preparation method comprises the following steps:
(1) using 99.99% -99.9999% of high-purity block simple substances Mn, Fe, P, Ge and Sn as raw materials, and putting the raw materials in an Ar gas-protected glove box according to Mn x2-Fe x P y1-Ge y Sn12Compounding, mixing and filling Al2O3In the crucible, fixing the crucible in a quartz tube by adopting quartz cotton, placing a separating device paved with the quartz cotton at the opening of the crucible, and sealing the quartz tube after filling Ar gas into the quartz tube;
(2) putting the sealed quartz tube into a muffle furnace, heating to 1173K from room temperature, preserving heat for 3-7 days to ensure that Mn, Fe, P and Ge are fully dissolved in Sn melt, then cooling to 573K at a cooling rate of 4-6K/h to ensure balanced and stable growth of crystals, taking the quartz tube out of the muffle furnace, inverting, pouring molten metal Sn, and fully filtering through quartz wool until the molten metal Sn is fully cooled;
(3) taking out the Sn-coated pseudo-single crystal, soaking the Sn-coated pseudo-single crystal in a 10% dilute hydrochloric acid solution for 1-2 weeks, filtering the solution, and cleaning the separated pseudo-single crystal for multiple times by using distilled water and alcohol to obtain needle-shaped Mn with mirror-surface luster on the surface5Ge3/(Mn, Fe)5Ge3A quasi-single crystal heterojunction.
CN201910742765.5A 2019-08-13 2019-08-13 Single crystal-like heterojunction room temperature magnetic refrigeration material with large magnetic entropy change and wide working temperature zone and preparation process thereof Active CN110556221B (en)

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CN103205590A (en) * 2013-04-27 2013-07-17 北京工业大学 Preparation process of magnetic refrigeration material
CN109576530A (en) * 2018-12-27 2019-04-05 江西理工大学 Huge exchange biased Mn based alloy of one kind and its preparation method and application
CN110052603A (en) * 2019-05-20 2019-07-26 北京工业大学 One kind is from Mn5Ge3The method that surface preparation has the micro-/ nano line of Sn@MnOx core-shell structure

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